CN106009921A

CN106009921A - Pigment dispersion for ink jetting, method of producing the same, ink set, and image forming method

Info

Publication number: CN106009921A
Application number: CN201610143526.4A
Authority: CN
Inventors: 藤井勇介
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-03-30
Filing date: 2016-03-14
Publication date: 2016-10-12
Anticipated expiration: 2036-03-14
Also published as: JP2016188345A; EP3075797B1; JP6227584B2; US20160289471A1; EP3075797A1; CN106009921B; US9879146B2

Abstract

A pigment dispersion for ink jetting, including: a pigment (A) represented by the following Formula (A); a pigment (B) represented by the following Formula (B); and water, wherein a content mass ratio of the pigment (A) to the pigment (B) is higher than 1.0. In Formula (A), each of two R 1 s represents a cyano group and each of two R 2 s represents a hydrogen atom, or each of two R 1 s represents a hydrogen atom and each of two R 2 s represents a tertiary butyl group. In Formula (B), each of two R3s represents a hydrogen atom and each of two R4s represents a chlorine atom, each of two R3s represents a hydrogen atom and each of two R4s represents a hydrogen atom, or each of two R3s represents a hydrogen atom and each of two R4s represents a phenyl group. The ink set uses the pigment dispersion for ink jetting.

Description

Ink-jet pigment dispersion and manufacture method, ink group and image forming method

Technical field

The present invention relates to ink-jet pigment dispersion and manufacture method, ink group and image forming method.

Background technology

In the image carried out by ink-jet method is formed, as ink, use the pigment disperseing pigment in a liquid Dispersion.

Such as, as employing the ink-jet as pigment of C.I. (Colour Index, pigment index) pigment orange 71 Ink, it is known that be the 1 of more than 4 containing C.I. pigment orange 71, carbon number, the oil of the ink-jet of 2-alkane glycol and specific alcoholic compound Ink (see, for example Japanese Unexamined Patent Publication 2013-91704 publication).

It addition, pigment is also used for the coloring of the middle color filters used such as liquid crystal indicator.

For example, as it is known that the red resin compositions that red pigment and C.I. pigment orange 71 are distributed in resin and Employ the manufacture method (see, for example Japanese Unexamined Patent Publication 11-310715 publication) of the color filter of this red resin compositions.

Summary of the invention

Invent problem to be solved

The ink-jet pigment dispersion (ink) of middle use is formed, from fall accordingly, as the image carried out by ink-jet method The viewpoints such as low environmental load and raising workability are set out, and as disperse medium, sometimes use the pigment dispersion of aqueous water system (ink).

But, in pigment, particularly C.I. pigment orange 71 and C.I. pigment orange 73 is and is difficult to be distributed to aqueous medium Pigment in (being the most sometimes also denoted as " water-medium ").Pigment dispersibility in water-medium is dispersed in water system with making pigment The storage stability of the pigment dispersion obtained in medium is relevant with ejection stability.

Therefore, for dispersible pigment dispersion (the such as Japanese Unexamined Patent Publication containing C.I. pigment orange 71 or C.I. pigment orange 73 and water Ink described in 2013-91704 publication), it is desirable to improve storage stability and ejection stability.

Here, " ejection stability " refers to stably spray the character of pigment dispersion from ink gun.Ejection is stable Property such as by evaluating from the character that ink gun sprays continuously i.e. " continuous ejection ".

It addition, the red resin compositions described in Japanese Unexamined Patent Publication 11-310715 publication is not the compositions of water system And be free from water and contain the compositions of the solvent system of solvent.Additionally, red described in Japanese Unexamined Patent Publication 11-310715 publication Chromoresin compositions is the red compositions with red pigment as main pigments.Therefore, Japanese Unexamined Patent Publication 11-310715 publication In, it is not concerned with 71 dispersibility in water-medium of C.I. pigment orange completely.

The present invention completes in view of the foregoing, and the present invention is to realize following purpose as problem.

That is, it is an object of the invention to, it is provided that storage stability and the ink-jet pigment dispersion of ejection excellent in stability And manufacture method and employ ink group and the image forming method of above-mentioned ink-jet pigment dispersion.

For solving the means of problem

As follows for solving the specific means of problem.

＜ 1 > a kind of ink-jet pigment dispersion, it contains pigment (A) that following formula (A) represents, following formula (B) represents Pigment (B) and water,

Described pigment (A) and described pigment (B) containing mass ratio more than 1.0.

In formula (A), about 2 R¹With 2 R², 2 R¹All represent cyano group and 2 R²All represent hydrogen atom or 2 R¹All Represent hydrogen atom and 2 R²All represent the tert-butyl group.

In formula (B), about 2 R³With 2 R⁴, 2 R³All represent hydrogen atom and 2 R⁴All represent chlorine atom, or 2 R³ All represent hydrogen atom and 2 R⁴All represent hydrogen atom, or 2 R³All represent hydrogen atom and 2 R⁴All represent phenyl.

＜ 2 > according to ＜ 1 > described in ink-jet pigment dispersion, wherein, described pigment (A) contains with described pigment (B's) Having mass ratio is 1.1～50.

＜ 3 > according to ＜ 1 > or ＜ 2 > described in ink-jet pigment dispersion, wherein, described pigment (A) and described pigment (B) be 1.1～25 containing mass ratio.

＜ 4 > according to ＜ 1 >～＜ 3 > according to any one of ink-jet pigment dispersion, wherein, described pigment (A) and institute State pigment (B) is 1.1～10 containing mass ratio.

＜ 5 > according to ＜ 1 >～＜ 4 > according to any one of ink-jet pigment dispersion, wherein, in formula (A), 2 R¹All Represent cyano group and 2 R²All represent hydrogen atom.

＜ 6 > according to ＜ 1 >～＜ 5 > according to any one of ink-jet pigment dispersion, wherein, in formula (B), 2 R³All Represent hydrogen atom and 2 R⁴All represent chlorine atom.

＜ 7 > according to ＜ 1 >～＜ 6 > according to any one of ink-jet pigment dispersion, wherein, in formula (A), 2 R¹All Represent cyano group and 2 R²All represent hydrogen atom；In formula (B), 2 R³All represent hydrogen atom and 2 R⁴All represent chlorine atom.

＜ 8 > according to ＜ 1 >～＜ 7 > according to any one of ink-jet pigment dispersion, it contains resin particle further Son.

＜ 9 > according to ＜ 1 >～＜ 8 > according to any one of ink-jet pigment dispersion, it contains resin dispersion further Agent.

＜ 10 > according to ＜ 1 >～＜ 9 > according to any one of ink-jet pigment dispersion, it contains water solublity further Solvent.

The manufacture method of ＜ 11 > a kind of ink-jet pigment dispersion, it is for manufacturing ＜ 1 >～＜ 10 > according to any one of The method of ink-jet pigment dispersion, it has:

By the most described pigment (A), described pigment (B) and water mix, carry out dispersion process obtain described ink-jet pigment The operation of dispersion.

＜ 12 > according to ＜ 11 > described in the manufacture method of ink-jet pigment dispersion, wherein, obtain described ink-jet face The operation of material dispersion comprises:

Described pigment (A) and described pigment (B) are mixed, obtain the step of pigment composition, and

The most described pigment composition and water are mixed, carries out dispersion and process the step obtaining described ink-jet pigment dispersion Suddenly.

＜ 13 > a kind of ink group, it comprises:

As ＜ 1 >～＜ 10 > according to any one of ink-jet pigment dispersion ink and

Treatment fluid containing the acid making the composition in described ink condense.

＜ 14 > a kind of image forming method, it has:

By ink-jet method using as ＜ 1 >～＜ 10 > according to any one of the ink of ink-jet pigment dispersion be imparted into Record on medium, operation bestowed by the ink of formation image, and

The treatment fluid on described record medium will be imparted into containing the treatment fluid of the acid making the composition in described ink condense Bestow operation.

Invention effect

According to the present invention, it is provided that storage stability and the ink-jet pigment dispersion of ejection excellent in stability and manufacturer thereof Method and employ ink group and the image forming method of above-mentioned ink-jet pigment dispersion.

Accompanying drawing explanation

Fig. 1 is the schematic configuration diagram of the configuration example representing the ink-jet recording apparatus used in the enforcement that image is formed.

Detailed description of the invention

Hereinafter, to ink-jet pigment dispersion and the manufacture method thereof of the present invention and employ above-mentioned ink-jet pigment The ink group of dispersion and image forming method are described in detail.

In this specification, use "～" numerical range that represents represent using "～" before and after described numerical value as Little value and maximum the scope being included.

In this specification, " (methyl) acrylic acid " for comprising the concept of both acrylic acid and methacrylic acid, " (methyl) Acrylate " for comprising the concept of both acrylate and methacrylate.

(ink-jet pigment dispersion)

The ink-jet pigment dispersion (being the most only designated as " pigment dispersion ") of the present invention represents containing following formula (A) Pigment (B) that pigment (A), following formula (B) represent and water, pigment (A) (is also denoted as " containing containing mass ratio with pigment (B) below Have mass ratio (pigment (A)/pigment (B)) ") more than 1.0.

In formula (A), about 2 R¹With 2 R², 2 R¹All represent cyano group and 2 R²All represent hydrogen atom, or 2 R¹All Represent hydrogen atom and 2 R²All represent the tert-butyl group.

In pigment (A), 2 R¹All represent cyano group and 2 R²The pigment all representing the mode of hydrogen atom is C.I. (Colour Index) pigment orange 71 (PO71).

In pigment (A), 2 R¹All represent hydrogen atom and 2 R²The pigment all representing the mode of the tert-butyl group is C.I. pigment orange 73(PO73)。

That is, pigment (A) is PO71 or PO73.

In pigment (B), 2 R³All represent hydrogen atom and 2 R⁴All the pigment of the mode of expression chlorine atom is C.I. paratonere 254 (being also denoted as " PR254 " below).

In pigment (B), 2 R³All represent hydrogen atom and 2 R⁴The pigment all representing the mode of hydrogen atom is C.I. paratonere 255 (being also denoted as " PR255 " below).

In pigment (B), 2 R³All represent hydrogen atom and 2 R⁴The pigment all representing the mode of phenyl is C.I. paratonere 264 (being also denoted as " PR264 " below).

That is, pigment (B) is PR254, PR255 or PR264.

It addition, the ink that the ink-jet pigment dispersion of the present invention is used as ink-jet (is also sometimes referred to as " ink combination Thing ").

As it has been described above, pigment (A) (PO71 or PO73) is the pigment being difficult to be dispersed in water-bearing media (water-medium).Cause This, for containing pigment (A) and the pigment dispersion of water, it is desirable to improve storage stability and ejection stability (is sprayed from ink gun The ejection stability gone out).

About this point, the pigment dispersion of the present invention, by containing pigment (B) outside pigment (A) further, and contains Pigment (A) and do not contain the pigment dispersion of pigment (B) and compare, storage stability and ejection stability improve.

Wherein, the ejection stability from ink gun ejection evaluates (reference by the continuous ejection sprayed from ink gun Embodiment described later).

The pigment dispersion utilizing the present invention obtains the reason of the effect above (storage stability and the raising of ejection stability) By being presumed as follows.

Pigment (A) and pigment (B) are as from knowable to formula (A) and formula (B), having identical skeleton (specifically for diketone Pyrrolopyrrole (DPP) skeleton).Pigment (A) is substituted substituent group (R on DPP skeleton with the difference of pigment (B)¹～R⁴) Kind.That is, pigment (A) be properly termed as with pigment (B) similar rather than pigment.Therefore consider, in the pigment dispersion of the present invention, Similar to pigment (A) rather than pigment (B) by as the synergist function for pigment (A), and containing pigment (A) Comparing when not containing pigment (B), the pigment (A) dispersion stabilization in water-medium improves.Pigment dispersion according to the present invention Body, it is considered to due to the raising of this dispersion stabilization, it is thus achieved that storage stability improves and sprays stability-enhanced effect.

It addition, in the pigment dispersion of the present invention, refer to this containing mass ratio (pigment (A)/pigment (B)) more than 1.0 Bright pigment dispersion is the pigment dispersion with orange form and aspect.

About these orange form and aspect, present inventor's result of study understands, is using containing the pigment (A) as orange pigment In the image formed with the pigment dispersion of the present invention of the pigment (B) as red pigment, and use containing pigment (A) not The image that pigment dispersion containing pigment (B) is formed is compared, it is thus achieved that what the vividness of orange form and aspect improved did not expect Effect.

Hereinafter, form and aspect, as long as no specified otherwise, refer to orange form and aspect, and form and aspect improve as long as no specified otherwise, refer to The vividness of orange form and aspect improves.

It addition, the pigment dispersion of the present invention can contain only a kind of pigment (A) (i.e. PO71 or PO73), it is also possible to containing 2 Plant (i.e. PO71 and PO73).

When the pigment dispersion of the present invention contains 2 kinds of pigment (A), the content (containing quality) of pigment (A) refers to 2 kinds of pigment (A) total content (always containing quality).

It addition, the pigment dispersion of the present invention can contain only a kind of pigment (B) (i.e. PR254, PR255 or PR264), also Two or more (i.e. two or more in PR254, PR255 and PR264) can be contained.

When the pigment dispersion of the present invention contains two or more pigment (B), the content (containing quality) of pigment (B) refers to 2 kinds The total content (always containing quality) of above pigment (B).

That is, this specification refers to always containing of at least one pigment (A) containing mass ratio (pigment (A)/pigment (B)) Quality is total containing mass ratio with the pigment (B) of at least one.

It addition, " pigment (A) and the total content of pigment (B) " described later refer to the total content of the pigment (A) of at least one with extremely The total of the total content of the pigment (B) of few a kind.

From the angle more effectively obtaining effect of the present invention, the pigment dispersion of the present invention preferably contains only a kind of face Material (A).

As containing mass ratio (pigment (A)/pigment (B)), go out from the viewpoint improving storage stability and form and aspect further Send out, preferably more than 1.1, more preferably more than 1.5, particularly preferably more than 2.0.

The upper limit containing mass ratio (pigment (A)/pigment (B)) is not particularly limited, from improve further storage stability, From the viewpoint of ejection stability and form and aspect, as containing mass ratio (pigment (A)/pigment (B)), preferably less than 50, more excellent Elect less than 25 as, more preferably less than 15, more preferably less than 10, more preferably less than 8.0, particularly preferably It is less than 6.0.

Containing mass ratio (pigment (A)/pigment (B)) from improving storage stability, ejection stability and form and aspect further Viewpoint is set out, and preferably 1.1～50, more preferably 1.1～25, particularly preferably 1.1～10.

The pigment dispersion of the present invention, from the viewpoint of the erasibility improving image further, preferably comprises resin particle Son.

It addition, generally, when pigment dispersion contains resin particle, do not contain resin particle phase with pigment dispersion Ratio, have the dispersion stabilization of pigment to reduce, the storage stability of pigment dispersion and ejection stability reduce tendency.

But, the pigment dispersion of the present invention is as noted previously, as and does not contains only pigment (A) possibly together with pigment (B), therefore Even if in the case of containing resin particle further, maintain the storage stability of pigment dispersion and ejection stable the most higher Property.In other words, when the pigment dispersion of the present invention contains resin particle further, do not contain with the pigment dispersion of the present invention Comparing during resin particle, the improvement effect (storage stability and the effect of ejection stability) that pigment (B) brings is significantly more Play (the improvement amplitude that i.e. pigment (B) brings increases).

Here, resin particle refers to by the particle of resin formation.

Resin particle for by this aspect of the particle of resin formation with by least some of cladding on pigment particles surface Pitch dispersant is different.

Above-mentioned resin particle, from the viewpoint of the dispersion stabilization improving this resin particle further, preferably has carboxyl Self-dispersing polymer particle.

The optimal way of the self-dispersing polymer particle with carboxyl is described later.

Hereinafter, each composition that can contain in the pigment dispersion of the present invention is illustrated.

＜ pigment >

The pigment dispersion of the present invention contains pigment (A) and pigment (B).

Pigment (A) is as it has been described above, be PO71 or PO73.As pigment (A), from dispersion stabilization and the face of pigment dispersion From the viewpoint of the form and aspect of material dispersion, particularly preferably PO71.

Pigment (B) is as it has been described above, be PR254, PR255 or PR264.As pigment (B), steady from the dispersion of pigment dispersion From the viewpoint of the qualitative form and aspect with pigment dispersion, particularly preferably PR254.

The particularly preferred mode of the pigment dispersion of the present invention is: pigment (A) is PO71 and pigment (B) is PR254's Mode.

Containing mass ratio (pigment (A)/pigment (B)), as mentioned above more than 1.0, preferably scope is also as described above.

Pigment (A) in the pigment dispersion of the present invention and the total content of pigment (B) from the viewpoint of image color, phase For the total amount of pigment dispersion, preferably 0.5 mass %～35 mass %, more preferably 1 mass %～30 mass %, enter one Step is preferably 1 mass %～20 mass %, more preferably 2 mass %～10 mass %, particularly preferably 2 mass %～6 Quality %.

The pigment dispersion of the present invention can also be containing other pigment in addition to pigment (A) and pigment (B).As other Pigment, can be from the known face described in Japanese Unexamined Patent Publication 2012-162655 publication, Japanese Unexamined Patent Publication 2013-47311 publication etc. Material suitably selects use.

But, from the viewpoint of more effectively obtaining effect of the present invention, the pigment dispersion of the present invention is the most substantially Do not contain other pigment in addition to pigment (A) and pigment (B).Containing sometimes, the content of other pigment is relative to pigment dispersion Total amount, below preferably 2 mass %, below more preferably 1 mass %, more preferably below 0.5 mass %.

＜ dispersant >

The pigment dispersion of the present invention preferably comprises and makes pigment (A) and pigment (B) scattered dispersant.

As dispersant, preferred resin dispersant.

As pitch dispersant, can be the water-soluble resin dispersant formed by water-soluble resin, it is also possible to for by non- The non-water-soluble resin dispersant that water-soluble resin is formed.

In this specification, " water solublity " refers to can dissolve the character of more than finite concentration in water.As " water solublity ", In the water 100g of 25 DEG C, preferably dissolve the character of more than 5g (more preferably more than 10g).

When the pigment dispersion of the present invention contains pitch dispersant, pitch dispersant preferably will be by pigment (A) and pigment (B) At least some of cladding on the surface of the pigment particles constituted.

Hereinafter, the most also at least one of the surface of the pigment particles being made up of pigment (A) and pigment (B) is divided by resin The particle of powder cladding is referred to as " resin-coating pigment particles ".

At least one of cladding on pigment particles surface can be passed through Japanese Unexamined Patent Publication 2009-190379 by pitch dispersant The known method such as the method described in publication is carried out.

Pitch dispersant preferably has at least one hydrophilic structure unit and at least one hydrophobic structure unit.

Here, as hydrophilic structure unit, the preferably containing at least construction unit of a hydrophilic radical.

As hydrophilic radical, nonionic group, carboxyl, sulfonic group, phosphate etc., preferably carboxyl can be listed.Its In, as nonionic group, hydroxyl, (nitrogen-atoms is unsubstituted) amide groups, oxidized olefin polymer (example can be listed As, polyoxyethylene, polyoxypropylene etc.) originate group, sugar alcohol source group etc..

Hydrophilic structure unit and hydrophobic structure unit containing mass ratio (hydrophilic structure unit: hydrophobic structure Unit) it is preferably the scope of the scope of 10:90～40:60, more preferably 10:90～30:70, is particularly preferably 10:90～25: The scope of 75.

As hydrophilic structure unit, it is however preferred to have the structure of acidic-group (such as carboxyl, sulfonic group, phosphate etc.) Unit, more preferably there is the construction unit of carboxyl.

As having the Component units of carboxyl, can list (methyl) acrylic acid, P-carboxy ethyl acrylates, fumaric acid, The Component units in the source such as itaconic acid, maleic acid .beta.-methylacrylic acid, wherein preferably (methyl) acrylic acid and P-carboxy ethyl acrylates come The construction unit in source, the further preferably construction unit in (methyl) acrylic acid source.

As hydrophobic structure unit, the construction unit in (methyl) acrylate source can be listed and containing aromatic series base The construction unit of monomer source.

Wherein, as hydrophobic structure unit, it is preferably selected from (methyl) acrylic acid C_1-20Arrcostab, (methyl) acrylic acid benzyl The construction unit that ester, (methyl) acrylate are originated with at least one in their derivant, further preferably The construction unit in (methyl) benzyl acrylate source.

Can be with a kind individually containing these hydrophobic structure unit in pitch dispersant, it is also possible to containing two or more.

As pitch dispersant, preferably use such as (methyl) acrylic acid-(methyl) benzyl acrylate copolymer, (first Base) acrylic acid-(methyl) acrylate copolymer, (methyl) acrylic acid-(methyl) acrylate- (methyl) acrylic acid C_1-20Alkyl ester copolymer etc..

Pitch dispersant, from the viewpoint of dispersibility, preferably has the hydrophilic structure unit of band carboxyl.

As the acid number of pitch dispersant, preferably 90mgKOH/g～150mgKOH/g, more preferably 100mgKOH/g～ 120mgKOH/g。

Wherein, acid number is measured by the method described in JIS standard (JISK0070,1992).

As the weight average molecular weight of pitch dispersant, preferably 1,000～100,000, more preferably 3,000～50, 000, more preferably 5,000～40,000.

Weight average molecular weight is measured by gel permeation chromatography (GPC).GPC uses HLC-8020GPC (TOSOH strain formula meeting Society's system), as chromatographic column, use TSKgel (registered trade mark) Super Multipore HZ-H (TOSOH Co., Ltd. system, 4.6mmID × 15cm) 3 pieces, as eluent, use THF (oxolane).It addition, as condition, making sample solution concentration is 0.45 Quality %, to make flow velocity be 0.35ml/ minute, makes sample injection rate is 10 μ l, makes mensuration temperature be 40 DEG C, uses RI detector to enter OK.It addition, standard curve is by TOSOH Co., Ltd. system " standard specimen TSK standard, polystyrene ": " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 ", " n-propylbenzene " these 8 samples make.

When the pigment dispersion of the present invention contains pitch dispersant, as containing of pigment (p) and pitch dispersant (s) Mass ratio (p:s), the scope of preferably 10:1～10:8, the more preferably scope of 10:1～10:7, more preferably 10:3 ～the scope of 10:7.

As the above-mentioned resin-coating pigment particles (pigment particles being made up of pigment (A) and pigment (B) under dispersity Surface at least some of by pitch dispersant cladding particle) volume average particle size, preferably 10nm～ 300nm, more preferably 50nm～250nm, more preferably 80nm～200nm.When volume average particle size is below 300nm, Color reproduction is good, carries out beating beating characteristic when dripping by ink-jet method and becomes good, and when for more than 10nm, light resistance becomes Well.

The volume average particle size of the resin-coating pigment particles under dispersity uses Nano Trak particle size distribution dress Put UPA-EX150 (Nikkiso Company Limited's system) to be measured by dynamic light scattering method.

＜ water >

The pigment dispersion of the present invention contains water.

That is, the pigment dispersion of the present invention is the compositions of water system.Therefore, the solvent system of solvent is contained with not containing water Compositions compare, reduce and this respect such as workability raising is favourable in carrying capacity of environment.

The content of the water in the pigment dispersion of the present invention is not particularly limited, relative to the total amount of pigment dispersion, excellent Elect more than more than more than 40 mass %, more preferably 50 mass %, more preferably 60 mass % as.

The upper limit of the content of the water in the pigment dispersion of the present invention is it is contemplated that the amount of pigment (A) and pigment (B) etc. is fitted Work as setting, the content of water relative to the total amount of pigment dispersion, below preferably 99 mass %, more preferably 95 mass % with Under, below particularly preferably 90 mass %.

＜ water-soluble solvent >

The pigment dispersion of the present invention, from the viewpoint of improving ejection stability further, preferably comprises water solublity molten Agent.

As water-soluble solvent, known water-soluble solvent can be used without particular limitation.

As water-soluble solvent, can list such as glycerol, 1,2,6-hexanetriols, trimethylolpropane, ethylene glycol, the third two The glycolss such as alcohol, diethylene glycol, triethylene glycol, TEG, five ethylene glycol, dipropylene glycol；2-butylene-1,4-glycol, 2-second Base-1,3-hexanediol, 2-methyl-2,4-PD, 1,2-ethohexadiol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl isophthalic acid, 2- The polyalcohols of the alkane glycol etc. such as pentanediol；The saccharide described in 0116th section of Japanese Unexamined Patent Publication 2011-42150 publication or sugar Alcohols, hyalomitome acids, carbon number be 1～4 alkyl alcohols, glycol ethers, 2-Pyrrolidone, N-methyl-2-pyrrolidine Ketone；Deng.

It addition, as water-soluble solvent, the compound that following structural formula (I) represents also can be listed.

In structure formula (I), the integer of the various expression more than 0 independently of l, m and n, and l+m+n=0～15 is satisfied.Wherein, l + m+n is preferably scope, the scope of more preferably 3～10 of 3～12.In structure formula (I), AO represents oxyethylene group or oxidation Acrylic.Wherein, preferential oxidation acrylic.During l+m+n >=2, the AO of more than 2 can be the same or different.

The oxyalkylene addition product of the compound represented as structure formula (I), preferably glycerine or glycerol.

Below, it is shown that the example of the compound that structure formula (I) represents.But, the present invention is not limited to these.Hereinafter, Numeral in bracket represents SP value.

·nC₄H₉O(AO)₄-H

(AO=EO or PO (EO:PO=1:1), SP value=20.1)

·nC₄H₉O(AO)₁₀-H

(AO=EO or PO (EO:PO=1:1), SP value=18.8)

·HO(A'O)₄₀-H

(A'O=EO or PO (EO:PO=1:3), SP value=18.7)

·HO(A”O)₅₅-H

(A " O=EO or PO (EO:PO=5:6), SP value=18.8)

·HO(PO)₃-H (SP value=24.7)

·HO(PO)₇-H (SP value=21.2)

1,2-hexanediol (SP value=27.4)

Wherein, EO, PO represent oxyethylene group, oxypropylene group respectively.

The oxyalkylene addition product of glycerol can also use the commercially available product listed.Such as, as polyoxyethyl propyl glycerol (polypropylene glycol and the ether of glycerol), can list SANNIX (registered trade mark) GP-250 (mean molecule quantity is 250), SANNIX GP-400 (mean molecule quantity is 400), SANNIX GP-600 (mean molecule quantity is 600) are (above by Sanyo's chemical conversion industry strain formula Commercial firm's system), LEOCON (registered trade mark) GP-250 (mean molecule quantity is 250), (mean molecule quantity is LEOCON GP-300 300), LEOCON GP-400 (mean molecule quantity is 400), LEOCON GP-700 (mean molecule quantity is 700) are (above by Lion Co., Ltd.'s system), polyglycerol glycol-three alcohol type (mean molecule quantity be 300, mean molecule quantity be 700) is (above by pure with light Medicine Industrial Co., Ltd system) etc..

When the pigment dispersion of the present invention contains water-soluble solvent, contained water-soluble solvent can simply be a kind and also may be used Think two or more.

The content of the water-soluble solvent in the pigment dispersion of the present invention (two or more time be total content) divides relative to pigment The total amount of a prose style free from parallelism, preferably 2 mass %～30 mass %, more preferably 5 mass %～30 mass %, more preferably 8 matter Amount %～30 mass %, particularly preferably 10 mass %～25 mass %.

＜ resin particle >

The pigment dispersion of the present invention preferably comprises at least one resin particle (i.e. by the particle of resin formation).Thus, figure The erasibility of picture more improves.

Particularly, the pigment dispersion of the present invention contains resin particle and uses this pigment dispersion and treatment fluid described later When forming image, the erasibility of image improves further.

More specifically, resin particle with record medium (particularly record medium in treatment fluid or make its be dried and The region become) contact time, owing in pigment dispersion, dispersion becomes unstable, cohesion occurs and viscosifies, therefore have pigment The immobilized function of dispersion.Thus, the erasibility of image more improves.Additionally, pigment dispersion is to recording the closely sealed of medium Property etc. the most more improves.

Wherein, resin particle for by this aspect of the particle of resin formation with resin-coating pigment particles phase mentioned above District.

It addition, during as it has been described above, the pigment dispersion of the present invention contains resin particle, with the pigment dispersion of the present invention not Compare during containing resin particle, the improvement effect (storage stability and the improvement effect of ejection stability) that pigment (B) is brought Play (the improvement amplitude that i.e. pigment (B) is brought is bigger) the most significantly.

As resin particle, from the viewpoint of dispersibility, it preferably is selected from polymer dispersion particle.

Self-dispersing polymer particle refers to the particle formed by self-dispersing polymer.

Self-dispersing polymer refers in the presence of not having surfactant, forms dispersity by phase transfer emulsion process Time, dispersity can be become in water-medium by functional group's (particularly acidic-group or its salt) of polymer self Insoluble polymer.

Here, the emulsifying shape that during dispersity is included in water-medium, insoluble polymer disperses with liquid condition State (emulsion) and insoluble polymer disperses with solid state in water-medium dispersity (suspension) this two The state of person.

Self-dispersing polymer from the viewpoint of pigment dispersion anchorage on the recording medium, preferably water-insoluble Polymer can be with the self-dispersing polymer of the dispersity of solid state dispersion.

Emulsifying or the preparation of dispersity, the i.e. aqueous dispersion of self-dispersing polymer as self-dispersing polymer Method, can list phase transfer emulsion process.As phase transfer emulsion process, can list and such as self-dispersing polymer dissolved Or after being distributed in solvent (such as hydrophilic organic solvent etc.), direct plunge into without surfactant in water, with will be from The state that the salt forming group (acidic-groups of such as carboxyl etc.) that polymer dispersion is had neutralizes stirs, mixing, by solvent After removing, the method obtaining becoming the aqueous dispersion of emulsifying or dispersity.

As self-dispersing polymer particle, can be from the 0090th～0121 of Japanese Unexamined Patent Publication 2010-64480 publication the Section, the of the 0130th～0167 section of Japanese Unexamined Patent Publication 2011-068085 publication and Japanese Unexamined Patent Publication 2011-62998 publication Self-dispersing polymer particle described in 0180～0234 section selects use.

(it preferably is from dispersibility polymerization as the resin constituting resin particle (preferably being from polymer dispersion particle) Thing), preferably comprise at least one in the construction unit in ester ring type (methyl) acrylate source, there is the chain that carbon number is 1～8 Shape alkyl (methyl) acrylate source construction unit at least one and carboxyl group-containing monomer source construction unit in The polymer (being also denoted as " polymer B " below) of at least one.

As ester ring type (methyl) acrylate, preferably following compound.

In ester ring type (methyl) acrylate, as monocyclic (methyl) acrylate, (methyl) acrylic acid can be listed Ring propyl ester, (methyl) acrylic acid ring butyl ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid The carbon number of the cycloalkyl such as cycloheptyl ester, (methyl) acrylic acid ring monooctyl ester, (methyl) acrylic acid ring nonyl ester, (methyl) acrylic acid ring ester in the last of the ten Heavenly stems It it is (methyl) acrylate ester etc. of 3～10.

In ester ring type (methyl) acrylate, as 2 ring types (methyl) acrylate, (methyl) acrylic acid can be listed different Norbornene ester, (methyl) acrylic acid norborneol ester etc..

In ester ring type (methyl) acrylate, as 3 ring types (methyl) acrylate, (methyl) acrylic acid gold can be listed Just alkyl ester, (methyl) acrylic acid bicyclopentane ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester etc..

Wherein, preferably 2 ring type (methyl) acrylate or 3 ring types (methyl) acrylate, more preferably (methyl) acrylic acid Isobornyl thiocyanoacetate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester or (methyl) acrylic acid bicyclopentane ester.

Content (2 kinds as the construction unit that ester ring type (methyl) acrylate of the total amount relative to polymer B is originated It is total content time above), preferably 20 mass %～90 mass %, more preferably 40 mass %～80 mass %, the most excellent Elect 40 mass %～70 mass %, particularly preferably 30 mass %～70 mass % as.

As having (methyl) acrylate of the chain-like alkyl that carbon number is 1～8, more preferably having carbon number is 1～4 (methyl) acrylate of chain-like alkyl, particularly preferably (methyl) acrylic acid methyl ester. or (methyl) ethyl acrylate.Here, chain Shape alkyl refers to the alkyl with straight or branched.

(methyl) acrylate source with the chain-like alkyl that carbon number is 1～8 as the total amount relative to polymer B The content (two or more time be total content) of construction unit, preferably 10 mass %～80 mass %, more preferably 20 mass % ～70 mass %, particularly preferably 20 mass %～60 mass %.

As carboxyl group-containing monomer, specifically, (methyl) acrylic acid .beta.-methylacrylic acid, itaconic acid, maleic acid, richness can be listed Horse acid, citraconic acid, 2-methacryloxymethyl succinic acid etc., particularly preferably (methyl) acrylic acid.

As the total amount relative to polymer B carboxyl group-containing monomer originate construction unit content (two or more time be total Content), preferably 1 mass %～30 mass %, more preferably 3 mass %～25 mass %, particularly preferably 5 mass %～20 Quality %.

(it preferably is from point as the resin constituting resin particle (preferably being from polymer dispersion particle, the most identical) Dissipate property polymer, the most identical) weight average molecular weight, preferably 3000～200,000, more preferably 10000～200,000, further It is preferably 30000～150,000.By making weight average molecular weight be more than 3000, it is possible to be effectively reduced water soluble ingredient amount.It addition, By making weight average molecular weight be less than 200,000, it is possible to increase self-dispersing stability.

It is same by the weight average molecular weight with above-mentioned pitch dispersant that weight average molecular weight may utilize gel permeation chromatography (GPC) The method of sample measures.

As constituting the acid number (KOHmg/g) of resin of resin particle, from the viewpoint of self-dispersing etc., preferably 20 Above and less than 200, more preferably more than 22 and less than 120, more preferably more than 25 and less than 100, particularly preferably More than 30 and less than 80.

Below, it is shown that constitute the object lesson of the resin of resin particle, but the present invention is not limited to these.Wherein, bracket The mass ratio of interior expression copolymer composition.

Methyl methacrylate/isobornyl methacrylate/methacrylic acid copolymer (20/72/8)

Methyl methacrylate/isobornyl methacrylate/methacrylic acid copolymer (38/52/10)

Methyl methacrylate/isobornyl methacrylate/methacrylic acid bicyclopentane ester/methacrylic acid is common Polymers (20/62/10/8)

Methyl methacrylate/methacrylic acid bicyclopentane ester/methacrylic acid copolymer (20/72/8)

As the scope of the volume average particle size of resin particle, preferably 10nm～400nm, more preferably 10nm～ The scope of the scope of the scope of 200nm, more preferably 10nm～100nm, particularly preferably 10nm～50nm.

The volume average particle size of resin particle can by with the resin-coating pigment particles under dispersity mentioned above The same method of volume average particle size measure.

When the pigment dispersion of the present invention contains resin particle (preferably being selected from polymer dispersion particle), divide relative to pigment The total amount of a prose style free from parallelism, the content of resin particle (two or more time be total content) is preferably 1～30 mass %, more preferably 2～20 matter Amount %, particularly preferably 2～10 mass %.

When above-mentioned content is more than 1 mass %, the erasibility of image more improves.

When above-mentioned content is below 30 mass %, it is possible to improve the ejection of ink further, and at suppression low temperature It is also advantageous on this aspect of the generation of the precipitate under environment.

＜ surfactant >

The pigment dispersion of the present invention can contain at least one surfactant as required.Surfactant such as may be used For use as surface tension modifier.

As surfactant, can be efficiently used and there is the structure holding hydrophilic portion and hydrophobic portion in intramolecular in the lump Compound, can arbitrarily use anionic surfactant, cationic surfactant, amphoteric surfactant, non-from Sub-property surfactant and betaine series surfactants.Further, it is also possible to above-mentioned pitch dispersant is used as surface activity Agent.

As surfactant, beat from the viewpoint of drip-dry disturbs from suppression ink, preferably nonionic surfactant, The most more preferably acetylenic glycols derivant (acetylenic glycols system surfactant).

As acetylenic glycols system surfactant, such as 2,4,7,9-tetramethyl-5-decine-4 can be listed, 7-glycol and 2, 4,7,9-tetramethyl-5-decine-4, the oxyalkylene addition product etc. of 7-glycol, it is preferably selected from least one therein.As these The commercially available product of compound, can list the E series of OLFINE (registered trade mark) E1010 etc. of such as Xin chemical industrial company.

As the surfactant in addition to acetylenic glycols system surfactant, preferably fluorine system surfactant.As fluorine system Surfactant, can list anion system surfactant, nonionic system surfactant, betaine series surfactants, The most more preferably anion system surfactant.As the example of anion system surfactant, CAPSTONE (note can be listed Volume trade mark) FS-63, CAPSTONE FS-61 (Dupont company system), FTERGENT (registered trade mark) 100, FTERGENT 110, FTERGENT 150 (NEOS company of Co., Ltd. system), CHEMGUARD (registered trade mark) S-760P (Chemguard Inc. company System) etc..

Time in pigment dispersion containing surfactant (surface tension modifier), carry out well from by ink-jetting style From the viewpoint of the ejection of pigment dispersion, preferably comprise can by the surface tension adjustment of pigment dispersion to 20mN/m～ The surfactant of the amount of the scope that 60mN/m adjusts, from capillary angle, more preferably 20mN/m～45mN/m, More preferably 25mN/m～40mN/m.

Here, the surface tension of pigment dispersion uses Automatic Surface Tensiometer CBVP-Z (association With interface science Co., Ltd. system) value of mensuration under conditions of liquid temperature is 25 DEG C.

When the pigment dispersion of the present invention contains surfactant, the Specific amounts of surfactant is not particularly limited, phase For the total amount of pigment dispersion, more than preferably 0.1 mass %, more preferably 0.1 mass %～10 mass %, the most excellent Elect 0.2 mass %～3 mass % as.

＜ carbamide >

The pigment dispersion of the present invention can contain carbamide.

Carbamide is high due to moisture-keeping functions, therefore as solid wetting agent, can effectively suppress ink less desirable be dried or Solidification.

When the pigment dispersion of the present invention contains carbamide, the content of carbamide relative to the total amount of pigment dispersion, preferably 1 More than quality % and below 20 mass %, it is more preferably below more than 1 mass % and 15 mass %, more preferably 3 matter Below amount more than % and 10 mass %.

Other compositions of ＜ >

The pigment dispersion of the present invention can also contain other compositions in addition to mentioned component as required.

As other compositions, can list solid wetting agent the most besides urea, Ludox, defoamer, inorganic salt, Anti-fading agent, emulsion stabilizer, impregnation-accelerator, UV absorbent, preservative, antifungus agent, pH adjusting agent, viscosity adjustment The known additive such as agent, antirust agent, chelating agen.

It addition, the pigment dispersion of the present invention can be the active energy ray containing at least one polymerizable compound (such as Ultraviolet) pigment dispersion of curing type.

Now, pigment dispersion preferably further contains (when using treatment fluid described later, in pigment dispersion and treatment fluid At least one) polymerization initiator.

As polymerizable compound, the 0128th～0144 section of such as 2011-184628 publication, Japan spy can be listed Open in the 0019th～0034 section of 2011-178896 publication or the 0065th～0086 section of Japanese Unexamined Patent Publication 2015-25076 etc. and remember The polymerizable compound (such as 2 officials can (methyl) acrylamide compound) above carried.

As polymerization initiator, can list the 0186th～0190 section of such as Japanese Unexamined Patent Publication 2011-184628 publication, The the 0126th～0130 section or the 0041st～0064 section of Japanese Unexamined Patent Publication 2015-25076 of Japanese Unexamined Patent Publication 2011-178896 publication Described in known polymerization initiator.

The preferred physical property of ＜ pigment dispersion >

The physical property of the pigment dispersion of the present invention is not particularly limited, preferably following physical property.

The pigment dispersion of the present invention from cohesion speed and compositions dispersion stabilization from the viewpoint of, preferably 25 DEG C PH under (± 1 DEG C) is more than 7.5.

About the pH (25 DEG C ± 1 DEG C) of pigment dispersion, preferably pH is 7.5～13, more preferably 7.5～10.

As the viscosity of the pigment dispersion of the present invention, from the viewpoint of cohesion speed, preferably 0.5mPa s～ The scope of 10mPa s, more preferably 1mPa s～the scope of 7mPa s.

Viscosity uses VISCOMETER TV-22 (TOKI SANGYO CO.LTD system) to measure under conditions of 30 DEG C.

As the pigment dispersion of the present invention surface tension under 25 DEG C (± 1 DEG C), preferably below 60mN/m, more excellent Elect 20mN/m～50mN/m, more preferably 25mN/m～45mN/m as.When the surface tension of pigment dispersion is at above-mentioned model When enclosing interior, record medium crimps and is inhibited, be therefore favourable.Surface tension uses Automatic Surface Tensiometer CBVP-Z (consonance interface science Co., Ltd. system) is measured by flat band method.

(manufacture method of ink-jet pigment dispersion)

As the method for the ink-jet pigment dispersion manufacturing the invention described above, the manufacturer of suitable implementation below Method.

That is, the manufacture method of the ink-jet pigment dispersion of present embodiment have by least pigment (A), pigment (B) and Water mixing, carry out dispersion and process and obtain the operation (being also denoted as " the 1st operation " below) of ink-jet pigment dispersion.

By the manufacture method of present embodiment, with manufacture respectively the dispersion that pigment (A) is dispersed in water and The dispersion being dispersed in water by pigment (B), the method that then they be mixed to get pigment dispersion are compared, pigment (A) excellent dispersion.Accordingly, it is capable to access storage stability and the pigment dispersion of ejection excellent in stability.

About pigment (A) and pigment (B) as described above, their preferred scope is also as described above.

The optimal way of the 1st operation is the mode comprising following step: pigment (A) and pigment (B) are mixed to get pigment The step of mixture and at least the above pigment composition and water are mixed, carries out dispersion and process and obtain ink-jet pigment dispersion Step.

By which, and manufacture the dispersion being dispersed in water by pigment (A) respectively and pigment (B) is dispersed in Dispersion in water, the method that then they be mixed to get pigment dispersion are compared, and the dispersibility of pigment (A) is the most excellent Different.Accordingly, it is capable to access storage stability and the pigment dispersion of ejection stability excellence especially.

But, the mode of the 1st operation is not limited to above-mentioned preferred mode, it is also possible to for adding at the same time or separately in water Pigment (A) and pigment (B), other modes such as mode then carrying out dispersion process.

Mixing and dispersion in 1st operation process and can carry out according to known maneuver.

Mixing and dispersion in 1st operation process and can use such as roll mill, triple-roller mill, ball mill, ball mill, rotating cylinder Sieve, dispersion machine, kneader, two-way kneader, homogenizer, mixer, single axle extruding machine, biaxial extruder etc..

Wherein, the details processed about mixing and dispersion, may further reference T.C.Patton and write " Paint Flow and Pigment Dispersion " record in (1964 John Wiley and Sons company periodical) etc..

It addition, in the 1st operation, will at least pigment (A), pigment (B) and water mix, but mixed object not only limiting In pigment (A), pigment (B) and water.In 1st operation, in addition to pigment (A), pigment (B) and water, it is also possible to mix other Point.

As other compositions, preferred dispersants (preferred resin dispersant).The preferred scope of dispersant is described above.

It addition, the manufacture method of present embodiment can also have the operation in addition to the 1st operation.

As the operation in addition to the 1st operation, can list in pigment dispersion (the ink-jet use obtained by the 1st operation Pigment dispersion) in the 2nd operation of further adding ingredient.

As the composition added in the 2nd operation, each one-tenth that can contain in pigment dispersion mentioned above can be listed Divide at least one in (such as water-soluble solvent, surfactant, carbamide, resin particle etc.).It addition, as in the 2nd operation The composition added, also can enumerate water outlet.

(ink group)

Ink that the ink group of present embodiment contains the ink-jet pigment dispersion as the invention described above and containing making The treatment fluid of the acid (being also denoted as " acid compound " below) of the composition cohesion in this ink.

By the ink group of present embodiment, it is possible to form the image that erasibility is excellent.

＜ treatment fluid >

Treatment fluid contains at least one acid compound.

(acid compound)

As acid compound, the acidic materials that the pH of ink can be made to reduce can be listed.

As acid compound, it is possible to use any one in organic acidity compound and inorganic acidic compound, also may be used With by least one in organic acidity compound and at least one in inorganic acidic compound.

-organic acidity compound-

As organic acidity compound, the organic compound with acidic-group can be listed.

As acidic-group, can list phosphate, phosphonate group, hypophosphorous acid base, sulfate, sulfonic group, sulfino and Carboxyl etc..In present embodiment, acidic-group from the viewpoint of the cohesion speed of ink, preferably phosphate or carboxyl, more It is preferably carboxyl.

There is organic compound (organic carboxyl acid) the optimization polypropylene acid of carboxyl, acetic acid, two alkyd, malonic acid, malic acid (preferably DL-malic acid), maleic acid, ascorbic acid, succinic acid, 1,3-propanedicarboxylic acid, fumaric acid, citric acid, tartaric acid, O-phthalic Acid, 4-methylphthalic acid, lactic acid, sulfonic acid, orthophosphoric acid, 2-pyrrolidone-5-carboxylic acid, pyrone carboxylic acid, pyrrol-carboxylic acid, furan carboxylic Acid, picolinic acid, coumarin acid, thiophene carboxylic acid, nicotinic acid or the derivant of these compounds or their salt are (the most Valency slaine) etc..These compounds can be with a kind of use, it is also possible to two or more is also used.

As organic carboxyl acid, from the viewpoint of the cohesion speed of ink, preferably carboxylic acid more than divalent (is also denoted as below Polybasic carboxylic acid), more preferably malonic acid, malic acid, maleic acid, succinic acid, 1,3-propanedicarboxylic acid, fumaric acid, tartaric acid, 4-methyl neighbour's benzene two Formic acid or citric acid, more preferably malonic acid, malic acid, tartaric acid or citric acid.

Preferred pKa is low for organic acidity compound.

Thus, contacted by the organic acidity compound lower with pKa, make to be disperseed by weakly acidic functional groups such as carboxyls The surface charge of the particles such as pigment in the ink of stabilisation or polymer particle reduces, it is possible to make dispersion stabilization reduce.

The preferred pKa of organic acidity compound contained by treatment fluid dissolubility low, in water is high, valence mumber is more than divalent, more Preferably have high than the pH region lower for pKa of the functional group of the particle decentralized stabilization made in ink (such as carboxyl etc.) The divalent of buffer capacity or the acidic materials of trivalent.

-inorganic acidic compound-

As inorganic acidic compound, phosphoric acid, nitric acid, nitrous acid, sulphuric acid, hydrochloric acid etc. can be listed, but limit the most especially Due to these.As inorganic acidic compound, from the sight of the cohesion speed that suppression and ink occur of the gloss uneven of image portion Point sets out, most preferably phosphoric acid.

Phosphoric acid dissolubility (25 DEG C) in forming calcium salt (calcium phosphate) Shi Shui is 0.0018g/ water 100g, less.Cause This, when the inorganic acidic compound contained by treatment fluid is phosphoric acid, calcium salt is insoluble and is immobilized, and suppression image portion surface occurs The excellent effect of generation of gloss uneven.

Particularly, as record medium, when using the record medium with the coating layer containing calcium carbonate, as treatment fluid Contained inorganic acidic compound, phosphoric acid is favourable.

The total amount of the acid compound contained by treatment fluid is not particularly limited, from the viewpoint of the cohesion speed of ink, Relative to the total amount for the treatment of fluid, preferably 5 mass %～40 mass %, more preferably 10 mass %～30 mass %.

When as acid compound by organic acidity compound and inorganic acidic compound used time, organic acidity compound With from cohesion speed and suppressing from the viewpoint of gloss uneven, relative to organic acidity chemical combination containing ratio of inorganic acidic compound Preferably 5 moles % of the content of the inorganic acidic compound of the content of thing～50 moles of %, more preferably 10 moles of %～40 rub You are %, more preferably 15 moles of %～35 moles of %.

Treatment fluid is in addition to acid compound, it is also possible to according to needing and with multivalent metal salt and/or cation property copolymer Composition is condensed Deng other.

About multivalent metal salt and cation property copolymer, such as Japanese Unexamined Patent Publication 2011-042150 publication can be used Multivalent metal salt described in 0155th～0156 section and cation property copolymer.

(water-soluble high-molecular compound)

Treatment fluid preferably comprises at least one water-soluble high-molecular compound.

As water-soluble high-molecular compound, it is not particularly limited, it is possible to use polyvinyl alcohol, polyacrylamide, poly-second The known water-soluble high-molecular compound such as alkene pyrrolidone, Polyethylene Glycol.

It addition, as water-soluble high-molecular compound, be suitable for use of specific macromolecular compound described later or Japan be special Open the water-soluble high-molecular compound described in the 0026th～0080 section of 2013-001854 publication.

The weight average molecular weight of water-soluble high-molecular compound is not particularly limited, and can be such as 10000～100000, excellent Elect 20000～80000, more preferably 30000～80000 as.

It addition, the content of the water-soluble high-molecular compound in treatment fluid is not particularly limited, total relative to treatment fluid Amount, preferably 0.1 mass %～10 mass %, more preferably 0.1 mass %～4 mass %, more preferably 0.1 mass % ～2 mass %, more preferably 0.1 mass %～1 mass %.

When content is more than 0.1 mass %, it is possible to promote further the extension that ink drips, when content be 10 mass % with Time lower, it is possible to suppress the thickening for the treatment of fluid further.It addition, when content is below 10 mass %, it is possible to further at suppression The crawling of the treatment fluid that the bubble in reason liquid causes.

As water-soluble high-molecular compound, preferably comprise and there is the hydrophilic of ionic group (preferred anionic group) The macromolecular compound (being also denoted as " specific macromolecular compound " below) of the construction unit of property.Thereby, it is possible to promote further The extension that the ink being imparted on record medium drips, suppression image is coarse further.

As the ionic group in specific macromolecular compound, can list carboxyl, sulfonic group, phosphate, boronate, Amino, ammonium or their salt etc..Wherein, preferably carboxyl, sulfonic group, phosphate or their salt, more preferably carboxyl, sulphur Acidic group or their salt, more preferably sulfonic group or its salt.

As having the hydrophilic construction unit of ionic group (preferred anionic group), preferably have ionic The construction unit in (methyl) acrylamide compound source of group (preferred anionic group).

As water-soluble high-molecular compound has the hydrophilic of ionic group (preferred anionic group) The content of construction unit, in the gross mass of water-soluble high-molecular compound, can be such as 10 mass %～100 mass %, It is preferably 10 mass %～90 mass %, more preferably 10 mass %～70 mass %, more preferably 10 mass %～50 Quality %, more preferably 20 mass %～40 mass %.

As specific macromolecular compound, more preferably comprise and there is above-mentioned ionic group (preferred anionic group, spy Preferably sulfonic group) hydrophilic construction unit at least one and hydrophobic construction unit at least one.Logical Crossing and comprise hydrophobic construction unit, specific macromolecular compound becomes easier to be present in treatment fluid surface, therefore bestow to The extension that ink on record medium drips is promoted further, the harsh feeling of image is suppressed more.

As hydrophobic construction unit, preferably (methyl) acrylate (preferably (methyl) acrylic acid C_1-4Arrcostab) The construction unit in source.

The content of the hydrophobic construction unit in specific macromolecular compound is in the gross mass of specific macromolecular compound In, can be such as 10 mass %～90 mass %, be preferably 30 mass %～90 mass %, more preferably 50 mass %～90 Quality %, more preferably 60 mass %～80 mass %.

(water)

Treatment fluid preferably comprises water.

The content of water relative to the gross mass for the treatment of fluid, preferably 50 mass %～90 mass %, more preferably 60 matter Amount %～80 mass %.

(water-soluble solvent)

Treatment fluid preferably comprises at least one in water-soluble solvent.

As water-soluble solvent, specifically, the water-soluble solvent that can be contained by the pigment dispersion of the present invention is same It is used in treatment fluid sample.

Wherein, from the viewpoint of suppression curling, preferably poly alkylene glycol or derivatives thereof, more preferably selected from two Ethylene glycol monoalkyl ether, triethylene glycol monoalky lether, dipropylene glycol, tripropylene glycol monoalky lether, polypropylene glycerol aether and poly- At least one in oxygen ethylene polyoxypropylene glycol.

As water-soluble solvent content in treatment fluid, from viewpoints such as coatings, overall relative to treatment fluid, excellent Elect 3 mass %～20 mass %, more preferably 5 mass %～15 mass % as.

-surfactant-

Treatment fluid can be containing at least one in surfactant.

Surfactant can be used as surface tension modifier.As surface tension modifier, nonionic table can be listed Face activating agent, cationic surfactant, anionic surfactant, beet alkali surface activator etc..Wherein, from ink Cohesion speed from the viewpoint of, preferably nonionic surfactant or anionic surfactant.

As surfactant, also can list page 37～38 of Japanese Laid-Open Patent Publication 59-157636 publication and The compound enumerated as surfactant in Research Disclosure No.308119 (1989).It addition, also can arrange Enumerate Japanese Unexamined Patent Publication 2003-322926, Japanese Unexamined Patent Publication 2004-325707, each publication of Japanese Unexamined Patent Publication 2004-309806 Described in fluorine (fluoroalkane base system) be surfactant and silicone based surfactants etc..

As the content of the surfactant in treatment fluid, being not particularly limited, the preferably surface tension for the treatment of fluid reaches To the content of below 50mN/m, more preferably reach 20mN/m～50mN/m content, more preferably reach 30mN/m～ The content of 45mN/m.

(other additives)

Treatment fluid as required can also be containing other compositions than that described above.

As other compositions that can contain in other compositions that can contain in treatment fluid, with pigment dispersion mentioned above It is same.

(physical property for the treatment of fluid)

Treatment fluid is from the viewpoint of the cohesion speed of ink, and the pH under 25 DEG C (± 1 DEG C) is preferably 0.1～0.5.

When the pH for the treatment of fluid is more than 0.1, the harsh feeling of record medium reduces further, the adaptation of image portion enters one Step improves.

When the pH for the treatment of fluid is less than 0.5, cohesion speed improves further, the ink dot of the ink that record on medium formation The unification of (ink ink dot) is inhibited further, the harsh feeling of image reduces further.

The pH (25 DEG C ± 1 DEG C) for the treatment of fluid more preferably 0.2～0.4.

As the viscosity for the treatment of fluid, from the viewpoint of the cohesion speed of ink, preferably 0.5mPa s～10mPa s Scope, more preferably 1mPa s～the scope of 5mPa s.Viscosity uses VISCOMETER TV-22 (TOKI SANGYO CO.LTD system) it is measured under conditions of 25 DEG C.

As treatment fluid surface tension under 25 DEG C (± 1 DEG C), preferably below 60mN/m, more preferably 20mN/m～ 50mN/m, more preferably 30mN/m～45mN/m.The surface tension for the treatment of fluid within the above range time, record medium in roll up Song is inhibited, and is favourable.The surface tension for the treatment of fluid uses Automatic Surface Tensiometer CBVP-Z (consonance interface science Co., Ltd. system) is measured by flat band method.

(image forming method)

The image forming method of present embodiment has: using the ink of the above-mentioned ink-jet pigment dispersion as the present invention Operation bestowed by the ink being imparted on record medium, being formed image by ink-jet method, and by containing the composition made in above-mentioned ink The treatment fluid that the treatment fluid of the acid of cohesion is imparted in aforementioned recording medium bestows operation.

By the image forming method of present embodiment, it is possible to form the image that erasibility is excellent.

As record medium, it is possible to use the most commercially available record medium, the such as " OK of Oji Paper PRINCE JOSHITSU ", " SHIRAOI (registered trade mark) " of Jujo Paper Co., Ltd, Jujo Paper Co., Ltd Good quality papers (A) such as " New NPI (registered trade mark) JOSHITSU ", " the OK EVER LIGHT (note of Oji Paper Volume trade mark) COAT ", micro-coated paper such as " the AURORA S " of Jujo Paper Co., Ltd；" the OK of Oji Paper COAT L ", the lightweight coated paper (A3) such as " the AURORA L " of Jujo Paper Co., Ltd；Oji Paper The coated paper (A2, B2) such as " the AURORA COAT " of " OK TOP COAT (registered trade mark)+", Jujo Paper Co., Ltd；King The art paper such as " OK gold rattan (registered trade mark)+" of Zi Zhi paper Co., Ltd. and " the special Pedicellus et Pericarpium Trapae ART " of Mitsubishi Paper Mills Limited (A1)；" NEW AGE (registered trade mark) ", " OK TOP COAT (registered trade mark) MAT " of Oji Paper, Japan " U-LIGHT (registered trade mark) " of Zhi Zhi Co., Ltd., " the NEW V MAT " of Mitsubishi Paper Mills Limited, in more Pulp industry Delustring paper (A2) such as " the white partridge MAT COAT N " of Co., Ltd.；" AIBEST (the registration of big Showa paperboard Co., Ltd. of Japan Trade mark) ", " the PERFECT W " of Hokuetsu Provincia de Kii Paper Co., Ltd, Oji Paper " BUON IVORY (note Volume trade mark)+", " the OK PLAU " of Oji Paper, " F1CARD ", the north of big Showa paperboard Co., Ltd. of Japan More " the NO BACK W " of Kishu Paper Co., Ltd., " HIGH LUCKY (registrar of Hokuetsu Provincia de Kii Paper Co., Ltd Mark) ", " the OK L CARD " of the Oji Paper, " PEARL DELUX (registrar of Mitsubishi Paper Mills Limited Mark) ", " the PC GREEN 100 ", " NewDV " of Hokuetsu Provincia de Kii Paper Co., Ltd of Oji Paper, north more records The ground paper etc. such as " UFCOAT " of " MARI COAT (registered trade mark) " of Zhou Zhi paper Co., Ltd., Oji Paper.

It addition, as record medium, it is also possible to use the various photo dedicated papers of ink mist recording.

Operation bestowed by ＜ ink >

Ink bestows operation for ink (pigment dispersion of the invention described above) is imparted into record medium by ink-jet method On operation.

In this operation, ink optionally can be imparted on record medium, form desired visual image.

The image carried out by ink-jet method is formed by giving energy, ink is ejected on desired record medium, Form rendered image.Wherein, as the preferred ink-jet method of present embodiment, Japanese Unexamined Patent Publication 2003-306623 publication can be applied The method described in the 0093rd～0105 section.

Ink-jet method is not particularly limited, and can such as utilize electrostatic attraction to make ink spray at random to use known mode The Charge controlled mode that goes out, drop on demand ink (drop on demand) mode (the pressure arteries and veins of the vibration pressure utilizing piezoelectric element Rush mode), the signal of telecommunication is changed into acoustic beam, irradiate ink and utilize radiation pressure make ink spray sound ink-jetting style and by oil Ink is thermally formed bubble, utilizes thermal inkjet (Bubble jet (the registered trade mark)) mode etc. of the pressure produced.As ink-jet method, Following ink-jet method can be effectively utilized especially: by the method described in Japanese Laid-Open Patent Publication 54-59936 publication, make to be subject to There is change in volume sharp in the ink of thermal energy effect, make under the effect of this state produced active force of change ink from Nozzle sprays.

As ink gun, have and use the serial head of short size, limit to make head enter along the width scanning limit of record medium The whole region on capable (shuttle) mode that comes and goes recorded and 1 limit employing and recording medium is arranged with record accordingly Line (line) mode of the line head (line head) of element.In line mode, by making record medium along first with record The scanning direction that the orientation of part intersects, it is possible to carry out image record, without scanning on whole of record medium The carrying system such as the paper advance mechanism (carriage) of short size head.It addition, also without paper advance mechanism movement and record medium Complicated scan control and only record medium and move, be therefore more capable of the high speed of writing speed than reciprocating manner.This The image forming method of invention at random to use these modes, but generally, can not carry out virtual ejection (dummy when being used in During line mode jet), the raising effect of the erasibility of ejection precision and image is big.

As the drop amount of the ink sprayed from ink gun, from the viewpoint of the image obtaining fine, preferably 1pl (picoliters)～10pl, more preferably 1.5pl～6pl.It addition, from the viewpoint of the connection improving image inequality, continuous tone, It is also effective for carrying out spraying by the combination of difference drop amount, even if in this case, present embodiment is suitable for use of.

＜ treatment fluid bestows operation >

In the image forming method of present embodiment, there is the treatment fluid being imparted into by treatment fluid on record medium and bestow work Sequence.

Treatment fluid bestows operation by being imparted into containing the treatment fluid of the acid compound making the composition in ink condense On record medium, treatment fluid and ink contact is made to carry out image conversion.Now, the dispersion with the resin particle in ink as representative Particle coacervation, image are immobilized on record medium.

Wherein, about the optimal way for the treatment of fluid, as mentioned above.

Bestowing for the treatment of fluid can use the known method such as rubbing method, ink-jet method, infusion process to carry out.As coating Method, can be by employing bar coater, extrusion die coating machine (extrusion die coater), Kohler coater, scraper plate painting It is known that cloth machine, bar are coated with machine, knife type coater, extrusion coated machine (squeeze coater), reverse roll coater, bar coater etc. Coating process is carried out.About the details of ink-jet method, as described above.

Treatment fluid is bestowed operation and can be at random arranged on before or after ink bestows operation.

In present embodiment, ink is preferably set after treatment fluid bestows operation and bestows operation.

Specifically, preferably before ink being imparted on record medium, bestow in advance for making the composition in ink The treatment fluid that (above-mentioned dispersed particle) condenses, then according to the mode contacted with the treatment fluid being imparted on record medium is bestowed Ink carries out the mode of image conversion.Thereby, it is possible to make ink mist recording high speed, it also is able to obtain dense even if carrying out high-speed record Degree, the image that resolution is high.

As the amount of bestowing for the treatment of fluid, as long as ink cohesion can be made then to be not particularly limited, preferably can make to be condensed into The amount of bestowing divided is 0.1g/m²Above amount.Wherein, the amount of bestowing preferably condensing composition reaches 0.2g/m²～2.0g/m²Amount. When the amount of bestowing of cohesion composition is 0.1g/m²Time above, it is possible to tackle the various use forms of ink and keep good high speed Coherency.It addition, the amount of bestowing of cohesion composition is 2.0g/m²Time following, do not have to the superficiality recording medium bestowed The angle of impact (change etc. of gloss) is set out, and is preferred.

It addition, in present embodiment, preferably arrange ink after treatment fluid bestows operation and bestow operation, liquid application will processed After giving on record medium, bestow period to ink, make the treatment fluid on record medium be dried (preferably heat drying).Thus, Being obtained in that preventing spreads and sinks in and blend the effect that ink colorant improves, it is as a result, it is possible to the good of record colour saturation and form and aspect can Visible image.Image in the optimal way of the heat drying mechanism for the treatment of fluid and the optimal way of method and drying process described later Heat drying mechanism and method be same.

＜ drying process >

The image forming method of present embodiment preferably have ink bestow operation and treatment fluid bestow operation after make figure As the drying process being dried.

It is dried as above-mentioned, preferably heat drying.

As the mechanism of the heat drying for carrying out image, known heating arrangements, the blowings such as heater can be listed The known wind pushing mechanism such as machine and the means that they are combined.

As the method for heat drying for carrying out image, can list such as from record medium and image forming surface Opposite side heater etc. apply heat method, blow to the image forming surface of record medium warm air or the method for hot blast, from The image forming surface of record medium or apply the method for heat with image forming surface opposite side infrared heater, they are multiple The method etc. combined.

The heating-up temperature during heat drying of image is preferably more than 60 DEG C, more preferably more than 65 DEG C, is particularly preferably More than 70 DEG C.

The upper limit of heating-up temperature is not particularly limited, and as the upper limit, can list such as 100 DEG C, preferably 90 DEG C.

The time of the heat drying of image is not particularly limited, preferably 3 seconds～60 seconds, more preferably 5 seconds～30 seconds, spy You Xuanwei 5 seconds～20 seconds.

＜ ink-jet recording apparatus >

The image processing system of the image forming method that can be used in present embodiment is not particularly limited, it is possible to use day This JP 2010-83021 publication, Japanese Unexamined Patent Publication 2009-234221 publication, Japanese Unexamined Patent Publication 10-175315 publication etc. Described in known image processing system.

Below, with reference to the example of ink-jet recording apparatus of the Fig. 1 image forming method to being adapted for carrying out present embodiment Son specifically illustrates.

Fig. 1 is to represent the schematic configuration diagram that ink-jet recording apparatus is integrally formed example.

As it is shown in figure 1, ink-jet recording apparatus towards record medium carrying direction (direction of arrow in figure) on successively It is equipped with the treatment fluid possessing the anilox roller 20 as the roller material for being coated with treatment fluid with the applicator roll 22 being in contact with it Bestow portion 12, possess the treatment fluid dry section 13 of heating arrangements (not shown) for making bestowed treatment fluid be dried, be used for The ink blowing unit 14 that various ink are sprayed and the ink setting district 15 of the ink setting being used for making ejection.

It is supplied to the record medium of this ink-jet recording apparatus under the effect of transport roller, from by having loaded record medium Box is sent to treatment fluid successively by the sheet feed section of supply record medium and bestows portion 12, treatment fluid dry section 13, ink blowing unit 14, ink setting district 15, is then collected at the portion of gathering.Carry in addition to using the method for transport roller, it is also possible to use and make use of The cylinder mode of transport of cartridge, belt mode of transport, employ the object stage mode of transport etc. of object stage.

In the transport roller of multiple configurations, at least 1 roller can be the driving roller of the power transmitting motor (not shown).Pass through The driving roller that motor carries out rotating is with constant speed rotary, so that record medium can be removed along the direction of regulation with the carrying amount of regulation Fortune.

Treatment fluid is bestowed and is provided with partial immersion in portion 12 and is being stored with the reticulate pattern ink transfer that configures of hold-up tank ground for the treatment of fluid Roller 20 and the applicator roll 22 contacted with anilox roller 20.Anilox roller 20 is for being supplied by the treatment fluid of prespecified amount The roller material of the applicator roll 22 configured in opposite directions with recording surface given to record medium.By the painting supplied in right amount from anilox roller 20 Cloth rewinder roll 22, treatment fluid is uniformly coated on record medium.

Applicator roll 22 is according to constituting with to the mode carrying record medium to roller 24 in couples, and record medium is from coating Roller 22 and between roller 24 by being sent to treatment fluid dry section 13.

It is configured with treatment fluid dry section 13 in the downstream in the record medium carrying direction that treatment fluid bestows portion 12.Treatment fluid Dry section 13 can use the known heating arrangements such as heater, the wind pushing mechanism that make use of the air-supply of hair-dryer etc. or it The mechanism that combines constitute.About heating arrangements, can list bestow with the treatment fluid of record medium that face is contrary one (such as when by record medium automatic transporting, mounting record medium carries out the lower section of the carrying mechanism carried) arranges heater in side Method Deng heater, the treatment fluid to record medium are bestowed face and are applied warm air or the method for hot blast, employ infrared heating The heating etc. of device, it is also possible to these method multiple combinations are heated.

It addition, along with the difference of the record kind (material, thickness etc.) of medium, ambient temperature etc., the surface of record medium Temperature also changes, and is the most preferably arranging the measurement portion measuring the surface temperature recording medium and will measure The value of surface temperature of the record medium that portion records feed back to the controlling organization of heating control section carry out temperature controlled in the case of Bestow treatment fluid.As the measurement portion that the surface temperature recording medium is measured, preferably contact or non-contacting thermometer.

Furthermore it is also possible to use solvent to remove roller etc., solvent is removed.As alternate manner, it is also possible to employing will with air knife The mode that remaining solvent removes from record medium.

Ink blowing unit 14 is arranged in the record medium carrying downstream, direction for the treatment of fluid dry section 13.Ink blowing unit 14 In be configured with and store each of black (K), cyan (C), magenta (M), yellow (Y), characteristic ink (A) and characteristic ink (B) Record head (ink ejection head) 30K, 30C, 30M, 30Y, 30A and 30B that each ink storage portion of color ink connects.Do not scheme The each ink storage portion shown is stored with the ink containing pigment, resin particle, water-soluble solvent and water corresponding with colors, When image record, supply as required to each ink ejection head 30K, 30C, 30M, 30Y.

In present embodiment, as any one in characteristic ink (A) and characteristic ink (B), use as the present invention's The ink (orange ink) of pigment dispersion.That is, as the present invention pigment dispersion ink from ink ejection with head 30A and Any one ejection in 30B.

In the ink-jet recording apparatus of present embodiment, another in ink ejection head 30A and 30B can omit.Separately Outward, except ink ejection is with in addition to head 30A and 30B, it is also possible to possess other characteristic ink ejection head.

Ink ejection with head 30K, 30C, 30M, 30Y, 30A and 30B from record medium with recording surface relative configuration spray Delivery nozzle is by the ink ejection corresponding with each image.Thus, each color ink is imparted on the recording surface of record medium, cromogram As being able to record.

Ink ejection head 30K, 30C, 30M, 30Y, 30A and 30B are the image recorded on record medium It is arranged with the whole line head (full line head) of multiple ejiction opening (nozzle) dominant record width (dominant record width). The round head width (side vertical with carrying direction in record medium carrying face along record medium of short size is made with limit To) shuttle-scanning, the limit head of serial type that carries out recording compares, it is possible to carry out image record the most at high speed.This In embodiment, although can by random use serial type record, maybe can carry out the record of higher speed in the way of such as 1 time Scanning i.e. forms the record of (single pass) mode of once passing through of 1 row, but according to the image record side of present embodiment Method, even if using One-through design also to be able to obtain the image of the high high-quality of repeatability.

Here, ink ejection head 30K, 30C, 30M, 30Y, 30A identical structure all with 30B.

The amount of bestowing for the treatment of fluid and the amount of bestowing of ink are adjusted the most as required.Such as can be according to record medium Difference, change treatment fluid the amount of bestowing, to regulate the physical property such as the viscoelasticity of the condensation product that treatment fluid and ink mix.

Ink setting district 15 is arranged in the record medium carrying downstream, direction of ink blowing unit 14.Ink setting district 15 can To be constituted in the same manner as treatment fluid dry section 13.

It addition, ink-jet recording apparatus can also configure record medium from sheet feed section to the transport path gather portion Implement the heating arrangements of heat treated.Such as can be by upstream side, ink blowing unit 14 and the oil at treatment fluid dry section 13 Ink dry section 15 between etc. desired position heating arrangements is set, make record medium be warming up to desired temperature, thus come high Effect be dried, fixing.

Embodiment

Hereinafter, by embodiment, the present invention is the most specifically illustrated, but as long as without departing from the purport of the present invention, Then the present invention is not limited to below example.Wherein, unless otherwise specified, " part " and " % " is quality criteria.

" dispersion liquid of resin-coating pigment particles " and " ink " in following example is the one of " pigment dispersion " Individual mode.

(embodiment 1)

The synthesis of ＜ water-soluble resin dispersant P-1 >

By methacrylic acid (172 parts), benzyl methacrylate (828 parts) and isopropanol (375 parts) are mixed, preparation Monomer supply compositions.It addition, by by 2,2-azo double (2-methylbutyronitrile) (22.05 parts) and isopropanol (187.5 parts) mix Close, prepare initiator supply compositions.

Then, isopropanol (187.5 parts) is heated to 80 DEG C under nitrogen atmosphere, dripped above-mentioned monomer with 2 hours wherein Supply compositions and the mixture of above-mentioned initiator supply compositions.Keep further after completion of dropwise addition to 80 DEG C 4 hours, then It is cooled to 25 DEG C.

After cooling, by solvent under reduced pressure remove, obtain weight average molecular weight and be about 30,000, acid number be the water-soluble of 112mgKOH/g Property pitch dispersant P-1.

The making of the dispersion liquid of ＜ resin-coating pigment particles >

In the water-soluble resin dispersant P-1 (150 parts) of above-mentioned acquisition, add potassium hydroxide aqueous solution, thus obtain pH It it is 9 and water-soluble resin aqueous dispersant that water-soluble resin dispersant concentration is 25 mass %.

It addition, by the pigment (A) shown in table 1 and pigment (B) according to the mass ratio (pigment (A)/pigment (B)) shown in table 1 Mixing, obtains pigment composition.

By above-mentioned water-soluble resin aqueous dispersant (97.2 parts), above-mentioned pigment composition (48.6 parts), water (78.2 Part) and dipropylene glycol (100 parts) mix, carry out dispersion process with ball mill (bead diameter be 0.1mm Φ, zirconium oxide beadlet), Obtain the resin-coating pigment particles that total content is 12 mass % of the pigment (A) relative to dispersion liquid total amount and pigment (B) Dispersion liquid (pigment dispersion).

The volume average particle size of the resin-coating pigment particles in the dispersion liquid that will obtain Nano Trak particle size distribution is surveyed Determine device UPA-EX150 (Nikkiso Company Limited's system) to be measured by dynamic light scattering method.Show the result in table 1.

The making of ＜ ink >

The following compositions of following composition is mixed, obtains ink (specifically for orange ink).

It should be noted that the ink obtained also is a mode of pigment dispersion.

-composition of ink (orange ink)-

＜ evaluates >

The ink obtained is used to carry out following evaluation.

Evaluation result is shown in table 1.

(evaluation of storage stability)

The ink 25g of above-mentioned acquisition is added in 30ml polyethylene bottle, then this polyethylene bottle is saved in setting In the temperature chamber of 60 DEG C 2 weeks.

Measure the viscosity of ink before and after above-mentioned preservation, calculate Δ viscosity according to the following formula.

Δ viscosity=(60 DEG C preserve the ink viscosity after 2 weeks)-(ink viscosity before preservation)

The mensuration of viscosity uses VISCOMETER TV-22 (TOKI SANGYO CO.LTD system) to be 30 in the temperature of ink Carry out under conditions of DEG C.

Based on the Δ viscosity obtained, according to following metewand, storage stability is evaluated.

Δ viscosity is the least, and the storage stability of ink is the most excellent, the most preferably.It addition, Δ viscosity is the biggest, the preservation of ink Stability is the poorest.

In following metewand, during for A, B, C, in being permissible range in practical.

-metewand of storage stability-

A: Δ viscosity≤0.3mPa s

B:0.3mPa s ＜ Δ viscosity≤0.6mPa s

C:0.6mPa s ＜ Δ viscosity≤1.0mPa s

D:1.0mPa s ＜ Δ viscosity≤2.0mPa s

E:2.0mPa.s ＜ Δ viscosity

(evaluation of continuous ejection)

As the evaluation of ejection stability, carry out the evaluation of continuous ejection shown below.

Prepare the printing head (GELJET (registered trade mark) GX5000) of Co., Ltd. Ricoh.

This printing head is fixed on and with the ink-jet recording apparatus shown in Fig. 1, there is the ink-jet recording apparatus equally constituted In.Printing head when this is fixing be configured to following configuration: the side of the line head of 96 nozzle arrangement of this printing head 75.7 ° are tilted to for the direction orthogonal relative to the moving direction same level of object stage.

Then, by the ink of above-mentioned acquisition from above-mentioned 96 nozzles with droplet of ink amount as 2pL, ejection frequency as 24kHz Ejection 45 minutes continuously.Wherein, confirm when this ejection starts that ink is from 96 whole nozzle ejections in advance.

After the continuous ejection of 45 minutes terminates, counting can be ejected into last nozzle number and (within 45 minutes, spray continuously and terminate After jetting nozzle number).Calculate ink emission rate with this jetting nozzle number by following formula, carry out oil according to following metewand The evaluation of the continuous ejection of ink.

Wherein, permissible in practicality it is classified as A, B and C person.

Ink emission rate (%)=(the jetting nozzle number after ejection terminated continuously in 45 minutes)/(total nozzle number) × 100

In above formula, total nozzle number is 96.

-metewand of continuous ejection-

Ink emission rate after ejection terminated continuously in A:45 minute is 100%.

Ink emission rate after continuously ejection terminated in B:45 minute is 98% less than 100%.

Ink emission rate after continuously ejection terminated in C:45 minute is 96% less than 98%.

Ink emission rate after continuously ejection terminated in D:45 minute is 94% less than 96%.

Ink emission rate after ejection terminated continuously in E:45 minute is less than 94%.

(evaluation of the vividness of form and aspect)

Use above-mentioned ink and above-mentioned ink-jet recording apparatus, spray volume is set as 2.0pL, whole orange image is retouched Paint OKTOP COAT (registered trade mark) 127gms (Oji Paper company system) and NPI (registered trade mark) FORM NEXT-IJ70 In each paper using of (Nippon Paper company system).

Whole the image that 5 estimators obtain with visualization, each estimator gives a mark according to following evaluation score.

Then, the average mark of the evaluation score of 5 estimators is obtained, based on the average mark obtained, according to following evaluation base Form and aspect are evaluated by standard.

-evaluation score-

5: whole image is the most bright-coloured orange form and aspect, and concentration is the denseest.

4: the orange form and aspect of whole image are bright-coloured, concentration is the denseest.

3: the vividness of the orange form and aspect of whole image is poor, concentration is the thinnest, but be practical permissible scope.

2: whole image does not has the vividness of orange form and aspect, concentration the thinnest, for bringing the quality of obstacle in practicality.

1: whole image is the thinnest entirely without vividness, the concentration of orange form and aspect, for bringing obstacle in practicality Quality.

-metewand of form and aspect-

The evaluation score of A:5 position estimator be equally divided into more than 4.5 and less than 5.0.

The evaluation score of B:5 position estimator be equally divided into 4.0 less than 4.5.

The evaluation score of C:5 position estimator be equally divided into 3.5 less than 4.0.

The evaluation score of D:5 position estimator be equally divided into 3.0 less than 3.5.

The average mark of the evaluation score of E:5 position estimator is less than 3.0.

(embodiment 2～9, comparative example 1 and 2)

Except the combination of the kind of pigment (A), the kind of pigment (B) and mass ratio (pigment (A)/pigment (B)) is changed Beyond the combination shown in table 1 below, carry out operation similarly to Example 1.

Embodiment 2～9 and comparative example 1 and 2 in, the total amount making pigment (A) and pigment (B) is same as in Example 1 Amount.

Particularly, in comparative example 1 and 2, pigment (B) is not used to use and the pigment (A) in embodiment 1 and pigment (B) The same amount of pigment of total amount (A).

Show the result in table 1.

Table 1

As shown in table 1, mass ratio (pigment (A)/pigment (B)) (i.e. the pigment in ink (A) and pigment (B) containing matter Amount than) (i.e. ejection is stable for the storage stability of the ink (pigment dispersion) of embodiment 1～9 more than 1.0 and continuous ejection Property, the most identical) excellent.

On the other hand, storage stability and the continuous ejection of the ink of comparative example 1 are poor, the ink of comparative example 2 continuous Ejection is poor.

Additionally, the image formed by the ink of embodiment 1～9 is compared with the image formed by the ink of comparative example 1 and 2, The vividness of orange form and aspect is the most excellent.

In the ink of embodiment 1～9, measure than (pigment (A)/pigment (B)) embodiment 2～9 in the range of 1.1～25 The storage stability of ink and continuous ejection the most excellent.

In the ink of embodiment 2～9, measure than (pigment (A)/pigment (B)) embodiment 3～9 in the range of 1.1～10 The continuous ejection of ink the most excellent.

(embodiment 101)

In addition to the composition of the ink in embodiment 4 is changed to following composition, carry out behaviour similarly to Example 4 Make.Show the result in table 2.

-composition of the ink (orange ink) of embodiment 101-

-making of self-dispersing polymer particle B-01-

Self-dispersing polymer particle B-01 makes as follows.

Butanone is added in the 2 liters of there-necked flasks possess blender, thermometer, reflux cooling pipe and nitrogen ingress pipe 560.0g is also warming up to 87 DEG C.Then, and in the case of the reflux state within keeping reaction vessel (following, maintain the reflux for state Until reaction terminates), the butanone in reaction vessel drips by metering system according to the mode constant speed being added dropwise to complete with 2 hours Acid methyl ester 220.4g, isobornyl methacrylate 301.6g, methacrylic acid 58.0g, butanone 108g and " V-601 " (with The polymerization initiator of Wako Pure Chemical Industries Co., Ltd.；Dimethyl 2,2 '-azo is double (2 Methylpropionic acid ester)) 2.32g composition Mixed solution.After completion of dropwise addition, stir 1 hour, then the solution after this stirring 1 hour is carried out the operation of following operation (1).

Operation (1): add the solution being made up of " V-601 " 1.16g and butanone 6.4g, stir 2 hours.

Then, it is repeated 4 times the operation of above-mentioned operation (1), then adds by " V-601 " 1.16g and butanone further 3 hours (operation so far is referred to as " reaction "), is stirred in solution, continuation that 6.4g is constituted.

After reaction terminates, by the greenhouse cooling of solution to 65 DEG C, add isopropanol 163.0g, let cool, thus contained The polymerization of methyl methacrylate/isobornyl methacrylate/methacrylic acid (=38/52/10 [mass ratio]) copolymer Solution (solid component concentration is 41.0%).

The weight average molecular weight (Mw) of above-mentioned copolymer is 63000, acid number is 65.1 (mgKOH/g).

Then, weigh the polymeric solution 317.3g (solid component concentration is 41.0%) obtained, be added thereto to isopropanol 46.4g, (aqueous acidic compound, is equivalent in terms of maleic acid 20% maleic anhydride aqueous solution 1.65g relative to copolymer 0.3%) the NaOH aqueous solution 40.77g of and 2 moles/L, is warming up to 70 DEG C by the temperature of liquid in reaction vessel.

Then, drip distilled water 380g to the solution being warming up to 70 DEG C with the speed of 10ml/ minute, carry out moisture dispersion (dispersion step).

Thereafter, under reduced pressure the temperature of liquid in reaction vessel is maintained at 70 DEG C, 1.5 hours, thus by isopropanol, first Ethyl ketone and distilled water total evaporate 287.0g (solvent removal step).PROXEL GXL (S) (Arch is added in the liquid obtained Chemicals Japan Co., Ltd. system) 0.278g (is calculated as with benzisothiazole-3-ketone relative to polymer solids composition 440ppm)。

Being filtered by the filter of liquid 1 μm obtained, filtrate reclaimed, thus obtaining solid component concentration is 26.5% The aqueous dispersion of self-dispersing polymer particle B-01.

The aqueous dispersion ion exchange water of the self-dispersing polymer particle B-01 obtained is diluted, thus prepares solid Body constituent concentration is the solution of 25.0%.The solution physical property that solid component concentration is 25.0% obtained is measured, result For pH be 7.8, electric conductivity be 461mS/m, viscosity be 14.8mPa s.

(embodiment 102, comparative example 101)

In embodiment 102, " dispersion liquid of the resin-coating pigment particles in embodiment 4 " in embodiment 101 is changed Dispersion liquid for the resin-coating pigment particles in embodiment 5；In comparative example 101, by embodiment 101 " in embodiment 4 The dispersion liquid of resin-coating pigment particles " dispersion liquid of resin-coating pigment particles that is changed in comparative example 1, in addition, Carry out the operation as embodiment 101.

Show the result in table 2.

Table 2

As shown in Table 1 and Table 2, containing resin particle (self-dispersing polymer particle, the most identical) and containing pigment (A) And the ink (with reference to table 2) not containing the comparative example 101 of pigment (B) does not contains with not containing resin particle and contain pigment (A) The ink (with reference to table 1) having the comparative example 1 of pigment (B) is compared, and storage stability and continuous ejection reduce further.

On the other hand, the ink (with reference to table 2) of the embodiment 101 containing resin particle, pigment (A) and pigment (B) with not Containing resin particle, the ink (with reference to table 1) containing pigment (A) and the embodiment 4 of pigment (B) shows that equal preservation is stable Property and continuous ejection.

Equally, the ink (with reference to table 2) of the embodiment 102 containing resin particle, pigment (A) and pigment (B) with do not contain The ink (with reference to table 1) of resin particle and embodiment 5 containing pigment (A) and pigment (B) maintain equal storage stability with Ejection continuously.

Confirmed by result above, when ink contains resin particle, when not containing resin particle with ink compared with, pigment (B) storage stability brought and the improvement effect of continuous ejection the most notable (amplitude of i.e. improving increases further).

(employing the example that the image for the treatment of fluid is formed)

Use the ink of the embodiment 101 and 102 containing resin particle and containing the acid making the composition in ink condense Treatment fluid forms image, thus with do not use compared with treatment fluid comes when image is formed, it is possible to improve further the anti-scratch of image Property.

(treatment fluid)

As treatment fluid, such as, can use the treatment fluid of consisting of.

About the physical property of the treatment fluid of consisting of, such as viscosity be 2.9mPa s (25 DEG C), surface tension be 41.0mN/m (25 DEG C), pH are 0.7 (25 DEG C).

Here, viscosity, surface tension and pH use respectively VISCOMETER TV-22 (TOKI SANGYO CO.LTD system), Automatic Surface Tensiometer CBVP-Z (consonance interface science Co., Ltd. system) and pH meter WM-50EG (east Sub-DDK Co., Ltd. system) it is measured.

-composition for the treatment of fluid-

Water-soluble polymer 1

Water-soluble polymer 1 can enter according to the 0200th～0204 of Japanese Unexamined Patent Publication 2013-001854 section and the 0229th section Row synthesis.

(image formation)

The example of the image forming method employing treatment fluid is as follows.

Co., Ltd.'s Ricoh GELJET (registrar is prepared in the same manner as the evaluation of the continuous ejection in embodiment 1 Mark) GX5000 printing head (i.e. the line head of 96 nozzle arrangement), this printing head is fixedly arranged on shown in figure 1 above The same composition of ink-jet recording apparatus ink-jet recording apparatus on.

As record medium, prepare such as OKTOP COAT (registered trade mark) (Oji Paper's system), enter successively Following treatment fluid bestows operation to row, operation bestowed by ink and drying process, forms image (record) on the recording medium.

-treatment fluid bestow operation-

To be fixed on the object stage of ink-jet recording apparatus, then as the OKTOP COAT (registered trade mark) of record medium The object stage being fixed with record medium is made linearly to move with 500mm/ second constant speed, simultaneously by above-mentioned treatment fluid wire rod Coating machine is according to reaching about 1.5g/m²Mode be applied to record on medium.

At the position bestowing end for the treatment of fluid, behind after end is bestowed at this position 1.5 seconds for the treatment of fluid, use hair-dryer Under conditions of 50 DEG C, start being dried for the treatment of fluid, terminate behind 3.5 seconds after treatment fluid bestows end to be dried.Now be dried Time is 2 seconds.

-ink bestow operation-

The record medium after the dry end for the treatment of fluid is made to move with object stage speed for 50mm/ second constant speed, simultaneously to executing The face of the treatment fluid having given record medium sprays the ink of embodiment 101 or 102 from above-mentioned printing head with line mode, forms figure Picture.Ink starts within being ejected in latter 2 seconds of the dry end for the treatment of fluid.

About the ejection condition of ink, such as to make droplet of ink amount be 3.5pL, ejection frequency is 24kHz, resolution is 1200dpi×1200dpi(dot per inch)。

-drying process-

Image after firm print is dried 10 seconds at 70 DEG C.

Thereby, it is possible to form the image that erasibility is excellent especially.

Claims

1. an ink-jet pigment dispersion, the pigment that it contains pigment (A) that following formula (A) represents, following formula (B) represents (B) and water,

Described pigment (A) and described pigment (B) containing mass ratio more than 1.0；

In formula (A), about 2 R¹With 2 R², 2 R¹All represent cyano group and 2 R²All represent hydrogen atom or 2 R¹All represent Hydrogen atom and 2 R²All represent the tert-butyl group；

In formula (B), about 2 R³With 2 R⁴, 2 R³All represent hydrogen atom and 2 R⁴All represent chlorine atom, or 2 R³All tables Show hydrogen atom and 2 R⁴All represent hydrogen atom, or 2 R³All represent hydrogen atom and 2 R⁴All represent phenyl.

Ink-jet pigment dispersion the most according to claim 1, wherein, described pigment (A) contains with described pigment (B's) Mass ratio is 1.1～50.

Ink-jet pigment dispersion the most according to claim 1, wherein, described pigment (A) contains with described pigment (B's) Mass ratio is 1.1～25.

Ink-jet pigment dispersion the most according to claim 1, wherein, described pigment (A) contains with described pigment (B's) Mass ratio is 1.1～10.

Ink-jet pigment dispersion the most according to claim 1, wherein, in formula (A), 2 R¹All represent cyano group and 2 R² All represent hydrogen atom.

Ink-jet pigment dispersion the most according to claim 1, wherein, in formula (B), 2 R³All represent hydrogen atom and 2 R⁴All represent chlorine atom.

Ink-jet pigment dispersion the most according to claim 1, wherein, in formula (A), 2 R¹All represent cyano group and 2 R² All represent hydrogen atom；In formula (B), 2 R³All represent hydrogen atom and 2 R⁴All represent chlorine atom.

Ink-jet pigment dispersion the most according to claim 1, it contains resin particle further.

Ink-jet pigment dispersion the most according to claim 1, it contains pitch dispersant further.

Ink-jet pigment dispersion the most according to claim 1, it contains water-soluble solvent further.

The manufacture method of 11. 1 kinds of ink-jet pigment dispersions, its ink-jet according to any one of manufacturing claims 1～10 By the method for pigment dispersion, it has:

The most described pigment (A), described pigment (B) and water are mixed, carries out dispersion and process and obtain described ink-jet pigment and disperse The operation of body.

The manufacture method of 12. ink-jet pigment dispersions according to claim 11, wherein, obtains described ink-jet pigment The operation of dispersion comprises:

The most described pigment composition and water are mixed, carries out dispersion and process the step obtaining described ink-jet pigment dispersion.

13. 1 kinds of ink groups, it comprises:

As the ink-jet pigment dispersion according to any one of claim 1～10 ink and

14. 1 kinds of image forming methods, it has:

Note will be imparted into as the ink of the ink-jet pigment dispersion according to any one of claim 1～10 by ink-jet method On recording medium, formed image ink bestow operation, and

The treatment fluid that treatment fluid containing the acid making the composition in described ink condense is imparted on described record medium is bestowed Operation.